JPH01216341A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic emulsion having an excellent rapid processing property and a high sensitivity and a less tendency for generating a fogging by existing a specified compd. from at the time of forming a silver halide particle having a high silver halide content to at the time of beginning a desalting of the particle and adding a silver halide solvent to the particle at the time of chemically sensitizing it. CONSTITUTION:The silver halide particle contd. in a silver halide emulsion layer is composed of the silver halide particle having a silver chloride content of >=90mol.%, and the compd. shown by formula I is existed in the prescribed period from the time of forming the silver halide particle to the time of beginning the desalting of the particle, and at least one kind of the silver halide solvent is added to the particle in the prescribed period of a chemical sensitizing step at the time of preparing the silver halide particle. In formula I, Q is a 5 or 6 membered heterocyclic ring group or a 5 or 6 membered heterocyclic ring group condensed with a benzene ring, M is hydrogen atom or a cation. Thus, the sensitive material having the excellent rapid processing property, the high sensitivity and the less tendency for generating the fog is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has excellent speed and stability, high sensitivity, low fog, and extremely little gradation fluctuation even when the temperature during exposure changes, and excellent stability. Regarding silver halide photographic materials, there are techniques that are particularly useful for color papers.

[Background of the invention]

In recent years, there has been an increasing demand for speeding up color development for various purposes including improving the productivity of photographic prints, and various measures have been taken for this purpose. One way to do this is to
It is known that color development can be accelerated by using a silver chloride emulsion or a silver chlorobromide emulsion with a high silver chloride content as a silver halide emulsion. For example, US Patent 4.
No. 183.756, No. 4,225.666, Japanese Unexamined Patent Publication No. 5
No. 5-26589, No. 58-91444, No. 5g-9
No. 5339, No. 5g-94340, No. 58-9573
No. 6, No. 58-106538, No. 58-107531
No. 58-107532, No. 58-107533, No. 58-108533, No. 58-125612, etc. have descriptions regarding the above technology.

The techniques described in these publications were quite satisfactory from the viewpoint of rapid processability, but silver halide emulsions containing high silver chloride have low intrinsic sensitivity, so they cannot be used at a level that does not pose a practical problem. It was difficult to sensitize. On the other hand, various sensitizing means have been proposed, including sulfur sensitization, gold sensitization, reduction sensitization, etc., and it is known that each of them can be used alone or in combination. In addition, a method of sensitizing by using a silver halide solvent in combination with the above-mentioned sensitization method is also known, and is disclosed in JP-A-55-2982.
No. 9, No. 55-77737, No. 58-30747, No. 60-80848, No. 60-225145, etc.

These are excellent techniques, but when applied to silver halide emulsions containing high silver chloride, although they do sensitize, they cause significant fogging, especially in the case of photosensitive materials for printing where white background is important. , turned out to be a fatal flaw. Therefore, in order to prevent the above-mentioned fogging, as an anti-fogging agent,
For example, the addition of azaindenes, triazoles, tetrazoles, imidazolium salts, etc., has been investigated as a means of improvement, but these antifoggants have the disadvantage that sensitivity decreases when used in large amounts, and the amount used is limited. , Due to limitations, the improvement effect is insufficient.

Furthermore, if the silver halide solvent described above is used for chemical sensitization, if the ambient temperature changes during exposure to produce prints (for example, changes in the mouth (morning and noon, summer and winter, etc., daily fluctuations, seasonal fluctuations), It has been found that the undesirable problem of gradation fluctuations occurs. Particularly, in the case of a multi-layer photosensitive material such as a photosensitive material for color printing, if the gradation of each layer fluctuates randomly, the color balance will be greatly disrupted, resulting in a significant drop in printing yield.

For these reasons, it has been difficult to put into practical use high silver chloride-containing silver halide emulsions that have high sensitivity, low fog, and high stability during exposure.

In order to eliminate the above-mentioned drawbacks, the inventors of the present invention have conducted extensive studies and found that a specific compound is made to exist between the time of formation of high silver chloride-containing silver halide grains and the start of desalting, and halogen is added during chemical sensitization. This book reveals the unexpected fact that by adding a silver halide solvent, it is possible to obtain a silver halide photographic emulsion that has excellent rapid processability, high sensitivity, low fog, and extremely little gradation variation due to temperature changes during exposure. This led to the invention.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a silver halide photographic material that has excellent rapid processability, high sensitivity, low fog, and extremely small gradation fluctuations with respect to temperature changes during exposure.

[Structure of the invention]

The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which the silver halide grains contained in the silver halide emulsion layer have a silver chloride content of 90 mol. % or more of silver halide grains at any time from grain formation to the start of desalting, and at least one of the silver halide solvents at any time during the chemical sensitization step. This is achieved by a silver halide photographic material characterized in that it is prepared by adding one type of silver halide.

General formula (S) In the formula, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with benzene rings, and M is a hydrogen atom or a cation. represents.

[Specific structure of the invention]

The silver halide grains contained in the silver halide photographic emulsion of the present invention are high silver chloride grains with a silver chloride content of 90 mol % or more, and from the viewpoint of rapid processability, the preferred silver chloride content is 99. It ranges from 0 mol% to 99.9 mol%.

The silver halide grains according to the present invention may be any of silver chlorobromide, silver iodochloride, silver chloroiodobromide, and silver chloride, and silver iodide may be contained, but the content is , preferably 1
mol% or less, more preferably 0.5 mol% or less,
Most preferably, it does not contain silver iodide. Therefore, preferred silver halide grains for the present invention are silver chlorobromide and silver chloride, and the most preferred grains are silver chlorobromide having the above-mentioned silver chloride content.

The silver halide grains according to the present invention may be used in combination with silver halide grains other than the present invention, but in that case, all the halides in the silver halide emulsion layer containing the silver halide grains according to the present invention The ratio of the projected area occupied by the silver halide grains of the present invention to the projected area occupied by the silver halide grains is preferably 50% or more, more preferably 75% or more.

The silver halide grains of the present invention can be used, for example, in JP-A-59-16
No. 2540, No. 59-48755, No. 60-2228
No. 44, No. 60-222845, No. 60-13673
It can be formed according to the method described in No. 5 and the like.

The grain size of the silver halide grains according to the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processing properties and sensitivity, it is preferably 0.2 to 1.6μ, more preferably 0. .25 to 1.2μ11 most preferably 0.5
The range is from 0.8μ to 0.8μ. The particle diameter can be measured by various methods commonly used in the technical field. Typical methods include Loveland's "Particle Size Analysis JA, S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122," or "Theory of Photographic Processes," co-authored by Mies and James. 3rd edition, published by Macmillan (
(1966), Chapter 2. The particle size can be measured using the particle's projected area or diameter approximation.

If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, rl represents the particle size on each side of the particle, and ni represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted to a circular image of the same area. .

The silver halide grains according to the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

The soluble silver salt and the soluble halide may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferred. Furthermore, as five types of simultaneous mixing method,
It is also possible to use the 6pAg-chondrold-double jet method described in No. 4.48521 and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal phase control agent such as a sensitizing dye may be used.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, US Pat. No. 4,183,756 and US Pat. No. 4,225.
No. 666, JP-A-55-26589, JP-A-55-4
2737, etc., and The Journal on Photographic Science (J, Photogr, 5ci) 2
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 1.39 (1973) and used. Furthermore, particles having twin planes or irregularly shaped particles may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains according to the present invention can be prepared by adding cadmium salt, zinc salt,
Metal ions can be added using lead salts, thallium salts, iridium salts, rhodium salts, iron salts, or complex salts thereof to be included inside the particles and/or on the particle surfaces, and in an appropriate reducing atmosphere. By leaving the particles in place, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

When removing unnecessary soluble salts from the emulsion of the present invention after the growth of silver halide grains is completed, the method described in Research Disclosure No. 17643 can be used.

The silver halide grains according to the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed.

In the present invention, the silver halide emulsion containing the silver halide grains according to the present invention has a solubility product (Ksp) with silver ions from the grain formation step to the start of the desalting step.
At least one compound selected from organic compounds represented by the general formula [5] having a solubility characteristic of 0-'' or less is added.

The desired effect cannot be expected with compounds that have a solubility product with silver ions other than the present invention that exceeds lXl0-'', that is, with compounds whose ability to form salts with silver ions is smaller. “New Experimental Chemistry Course 1
You can refer to Volume # (published by Maruzen), pages 233 to 250.

In the present invention, the solubility product with the silver ion is lXl0
-” The organic compound having the following solubility characteristics (hereinafter referred to as the organic compound of the present invention) is preferably an organic compound having the following general formula [S]
This is a mercapto compound represented by

In the formula, Q represents a 5- or 6-membered heterocycle or an atomic group necessary to form a 5- or 6-membered heterocycle fused with benzene rings, and M represents a hydrogen atom or a cation.

The mercapto compound represented by the general formula [S] that is preferably used as the organic compound of the present invention will be described below.

In the general formula [3], Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with benzene rings; Examples of the ring include an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, etc. can be given.

Examples of the cation represented by M include alkali metals (
Examples include sodium, potassium, etc.), ammonium groups, and the like.

The mercapto compound represented by the general formula [5] can be further synthesized by the following general formulas [SA, ], [SBJ, [SC] and [SD
] Preferred are mercapto compounds represented by the formulas respectively.

In the formula, RA represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group,
2 is -NH-, -0-. or -S-, and M has the same meaning as M in the general formula [S].

General formula [SB] +' In the formula, Ar represents, and RB is an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group, a carbamoyl group, or a sulfonamide group. represents. n represents an integer from θ to 2. M has the same meaning as M in general formula [5].

In general formulas [SA] and [SB], RA and R
Examples of the alkyl group represented by 11 include methyl group, ethyl group, butyl group, etc., examples of alkoxy groups include methoxy group, ethoxy group, etc., and examples of salts of carboxyl group or sulfo group include sodium salt,
Examples include ammonium salts.

In the general formula [SA], examples of the aryl group represented by RA include a phenyl group and a naphthyl group, and examples of the halogen atom include a chlorine atom and a bromine atom.

In the general formula [SB], examples of the acylamino group represented by R8 include a methylcarbonylamino group and a benzoylamino group, examples of the carbamoyl group include an ethylcarbamoyl group and a phenylcarbamoyl group, and examples of the sulfonamide group include Examples include methylsulfonamide group and phenylsulfonamide group.

The above-mentioned alkyl groups, alkoxy groups, aryl groups, amino groups, acylamino groups, carbamoyl groups, sulfonamide groups, etc. further include those having substituents.

Represented by the general formula [SO3. RA represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -5RA, or a terocyclic group, and RAl represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, CORA4
．． or -5O*RAi, R12 and RA3 represent a hydrogen atom, an alkyl group, or an aryl group, and RA
4 and RA represent an alkyl group or an aryl group.

M has the same meaning as M in general formula [S].

General formula [RA in SO3, RA,, RA,,
RAM.

Examples of the alkyl groups represented by RA4 and RAM are:
Examples of the aryl group include a methyl group, a benzyl group, an ethyl group, a propyl group, and the like, and examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the alkenyl group represented by RA and RAI include a propenyl group, and examples of the cycloalkyl group include a cyclohexyl group.

Examples of the heterocyclic group represented by RA include furyl group and pyridinyl group.

The above RA, RA1. RAz, RAs, RA4 and RA
, the alkyl group and aryl group represented by , the alkenyl group and cycloalkyl group represented by RA8 and RAl, and the heterocyclic group represented by RA are further represented by the general formula [S
D] ■ In the formula, RA and M each represent the same groups as RA and M in the general formula [SO3.

Further, Ro and R□ each represent a group having the same meaning as RAl and RAM in the general formula [sC].

Specific examples of the compound represented by the general formula [S] are shown below, but the present invention is not limited thereto.

SA-ISA-2 SA-3SA-4 5A-5SA-6 SA-7SA-8 SR-1sB-2 SB-3SB-4 SB-55B-6 1'. Below 1 margin or - 1/ Below margin - The compound represented by the above general formula [5] is described in, for example, Japanese Patent Publication No. 40.28496, Japanese Patent Application Publication No. 50.89034, Journal on Chemica J Research Society ( J.Chem.
Soc, ) 49.1748 (1927), 4237 (
1952), Journal on Org Chemistry (J, Org, Che-,) 39.2469 (
1965), U.S. Patent No. 2,824.001, Journal on Chemical Society, 1723 (195
1), Japanese Patent Application Publication No. 56-111846, British Patent No. 1,27
No. 5,701, U.S. Pat. No. 3,266.897, U.S. Patent No. 2.
403.927, etc., and can be synthesized according to the methods described in these documents.

In order to incorporate the compound represented by the general formula [S] according to the present invention (hereinafter referred to as compound [51]) into a silver halide emulsion containing silver halide grains according to the present invention, it is necessary to add water or water. Optionally miscible organic solvents (e.g. methanol,
ethanol, etc.) and then added. Compound [51 may be used alone, or in combination with two or more compounds represented by general formula [5], or in combination with other stabilizers or fog suppressants other than the compound represented by general formula [31]. May be used.

Compound [31 may be added at any time between the silver halide grain formation step and the start of the desalting step, but this step will be described in detail here. In a preferred embodiment of the present invention, the silver halide forming step is a 91g-chondrold double jet method, in which a silver ion-containing solution and a halogen-containing solution are injected until grain formation is completed.

Since the silver halide emulsion containing silver halide grains formed in this way usually contains unnecessary soluble salts, the salts must be removed to prevent them from causing failure in subsequent processes and after the product is made. Perform the operation. This is generally called a desalination process.

In the desalting process, a suitable precipitating agent is added to the silver halide emulsion to coagulate gelatin, thereby settling the silver halide grains, draining the supernatant, and adding washing water to dilute the soluble salts. do.

Next, by adding a suitable precipitant and repeating the above operation, it becomes possible to significantly reduce the concentration of the soluble salts originally contained.

However, due to the operation of the desalting step, not only soluble salts but also gelatin flow out at the same time, so that the gelatin concentration in the silver halide emulsion ultimately decreases. The process of adding additional gelatin to compensate for this and mixing it with the silver halide emulsion coagulated in the desalting process is called a redispersion process.

By performing this operation, silver halide grains are dispersed in gelatin at an appropriate concentration, making it possible to prepare a uniform silver halide emulsion without grain agglomeration or grain imbalance. Become.

Compound [S] may be added into the reaction vessel before silver halide formation, or may be added from the initial stage of grain formation until the final grain size is reached, or after grain formation and after the start of the desalting process. You can. However, if it is added after the start of the desalting process, for example during the desalting process or during the redispersion process, the effects of the present invention cannot be obtained.

Therefore, the compound [S] may be added in its entirety at one time, divided into multiple times, or added continuously during the particle formation step and before the start of the desalting step.

The most suitable addition times for exhibiting the effects of the present invention are a method of adding continuously during the silver halide grain formation process, and a method of adding immediately after the formation of silver halide grains (within about 5 minutes).

There is no particular restriction on the amount added, but it is usually 1 x 10-' mol to 1 x 10 mol per mol of silver halide, preferably 1 x 10-' mol to I x 10
−” added in the molar range.

The silver halide emulsion according to the present invention is chemically sensitized in the presence of a silver halide solvent.

The silver halide solvent used in the present invention includes:
A compound that reacts with silver halide to form a water-soluble silver salt is used, but in the case of a sulfide-containing metal, a compound that does not form silver sulfide is used. For example, ammonium thiocyanate or alkali metal salts (potassium thiocyanate, sodium thiocyanate), thiourea derivatives (tetrasubstituted thioureas such as tetramethylthiourea, which do not react with silver salts to form silver sulfide), etc. are preferably used. , ammonia, amine derivative (triethylenetetramine),
Compounds capable of forming a complex with silver halide, such as nitrogen-containing heterocyclic compounds such as pyridine and imidazole, and derivatives thereof, can also be used.

Next, typical examples of the above silver halide solvent will be shown, but the invention is not limited thereto.

(Exemplary compounds) 1) KSCN 2) Na5CN
3) NH4SCN In the present invention, thiocyanates such as thiocyanic acid, potassium thiocyanate and ammonium thiocyanate are particularly preferably used as the silver halide solvent.

The silver halide solvent used in the present invention may be added before chemical sensitization of the photographic emulsion or may be added during chemical ripening, but at least 80% of the chemical sensitization process is carried out.
In order to obtain the effects of the present invention, it is preferable to add it before the process is completed. The above-mentioned solvent can be added to the emulsion in a mixture with other sensitizers (for example, gold salt), but it is preferable to add it separately from other sensitizers. In this case, it does not matter which order of addition is added first.

In the present invention, the amount of the silver halide solvent added can vary widely depending on the type of solvent, desired effect, etc., and is generally about I x 10-' mol to I x 10 per mol of silver halide. -' molar range, preferably about I x 10-' moles to l x 10-' moles.

The silver halide emulsion according to the present invention can be subjected to conventional chemical sensitization, that is, sulfur sensitization, gold sensitization, ring element sensitization, and noble metal sensitization. Preferably, unstable sulfur compounds and gold compounds are used. chemically sensitized in the presence of

The unstable sulfur compound and gold compound preferably used in the present invention will be explained below.

The unstable sulfur compound used in the present invention is a sulfur-containing compound that has the property of forming a silver salt when reacting with silver halide and further forming silver sulfide under strong alkaline conditions, for example. Mention may be made of sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, and the like.

The amount of the sulfur sensitizer which is the unstable value and yellow compound used in the present invention varies depending on various conditions, but ranges from 1 x 10-' mol to 1 x 10-' mol per 1 mol of silver halide.
It is preferably used in a molar range, more preferably l x 10-' mol to t x to-' mol, particularly preferably 2 x 10-' mol to 8 x 107' mol.
It is a mole. Further, when the above-mentioned sulfur sensitizer is added to an emulsion, it may be added after being dissolved in water or an alcohol such as methanol or ethanol.

Examples of the gold compound used in the silver halide emulsion layer of the present invention include chloroauric acid, sodium chloroaurate, and gold potassium thiosulfate.

However, it is not limited to these.

The amount of the gold compound according to the present invention added is preferably 1 x 10-' to 5 x 1 G-' mol per 1 mol of silver halide, more preferably 2 x 10-' to 1 x 10-' mol, and Preferably 2.6X 10-@~
4 X 10-', most preferably 2.6X 10-'
9 x 10-'.

The gold compound according to the present invention may be added from the time when the silver halide grains according to the present invention are formed until the chemical sensitization is completed.

The unstable sulfur compound and gold compound according to the present invention need only be present during chemical sensitization of the high silver chloride grains according to the present invention, and specifically, from the end of the formation of the grains to the end of chemical sensitization. be added to and present.

In the silver halide emulsion of the present invention, compounds called antifoggants and stabilizers are added in order to optimally apply chemical sensitization and to prevent a decrease in sensitivity and the occurrence of fog during storage or development of the light-sensitive material. be able to.

These compounds include 4-hydroxy-6-methyl-1゜3,3a, 7-tetrazaindene, 3-methylbenzothiazole, l-phenyl-5-mercaptotetrazo-J, and many other heterocyclic compounds. compounds, mercapto compounds, etc. are known, but in the present invention, the general formula (S
) are particularly preferably used.

Compound [5] is generally added at the end of chemical sensitization of silver halide, but it can be added at the beginning or in the middle of chemical sensitization after the formation of silver halide grains. is also possible. The most preferable method for enhancing the effect of the present invention is to add it in portions at the start and end of chemical sensitization.

There is no particular restriction on the amount added, but it is usually l x 10-' mol to I x 10-' mol per mol of silver halide.
'moles, preferably I X 10-'mols to lXl0
- It is added in the range of 1 mol.

Further, in the present invention, it is preferable to add a water-soluble bromide after the completion of chemical sensitization in order to further enhance the effects of the present invention.

Various water-soluble bromides are used, but typical examples include ammonium, potassium, sodium,
Inorganic bromides and organic bromides of lithium and strontium, such as tetraethylammonium bromide, ethylpyridium bromide, and cetyltrimethylammonium bromide, are used.

The amount added varies widely depending on the halogen composition of the silver halide emulsion used, the properties of silver halide grains such as crystal phase, and the time of addition, but it is 2XlG-6 per mol of AgX.
~5 X 10-' mol, preferably 2XlO-6~I
XIG-” moles.

It is not preferable to add it before the end of chemical ripening. That is, for example, if bromide is added during chemical ripening, the ripening itself will be greatly affected by bromide, resulting in undesirable performance.

Opening may be carried out at any time from the end of chemical ripening until the silver halide emulsion layer is formed. For example, it may be added to other layers, such as a layer adjacent to the silver halide emulsion layer, and then diffused and supplied during multilayer coating. It is preferably added from the time of preparing the silver halide emulsion coating solution to immediately before coating.

When preparing a coating solution, a silver halide emulsion, a coating aid (for example, a spreading agent such as an anionic, cationic, nonionic, or amphoteric surfactant, an unsaturated monomer having an active ester group such as N-acryloyloxysuccinimide, Copolymers with ethylenically unsaturated monomers, liquid physical property conditioners represented by thickeners such as poly(styrene-maleic anhydride), poly(ethyl acrylate-maleic anhydride), etc.) and pigments. Now is the time to prepare the coating solution by mixing the forming coupler, stabilizer, etc. When added at this time, the water-soluble bromide of the present invention may be added after all of the coating additives have been added, or may be added during the addition. Additionally, any additive that does not react with the water-soluble bromide may be added during the addition. Furthermore, a water-soluble bromide may be added in advance to a container in which the coating solution is prepared, and the silver halide emulsion and additives may be added therein.

The emulsion according to the present invention can be spectrally sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

When the silver halide emulsion according to the present invention is used as a blue-sensitive emulsion, it is preferable to perform spectral sensitization with a sensitizing dye represented by the following general formula [A].

General formula [A] In general formula [A], 211 and zl! are the atoms necessary to form a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus, a pyridine nucleus, or a quinoline nucleus, respectively. represents a group, and these heterocycles also include those having substituents.

2, and ZI! The substituent of the heterocycle formed by is a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group.

R□ and R1 each represent an alkyl group, an alkenyl group, or an aryl group, preferably an alkyl group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably an alkyl group substituted with a carboxyl group or a sulfo group. It is a sulfoalkyl group having 1 to 4 atoms.

Further, R13 is selected from a hydrogen atom, a methyl group, and an ethyl group.

xe represents an anion, and a represents 0 or l.

Among the sensitizing dyes represented by the general formula [A], particularly useful dyes are the sensitizing dyes represented by the following general formula [A'].

General formula [A'1] Here, Yl and Y each represent an atomic group necessary to complete a benzene ring or a 7talene ring, which may be substituted.

The benzene ring and naphthalene ring formed by Y and Y may have a substituent, and the substituent is preferably a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.

R2,, R2□, R2,, xe and Q are general formula [A]
This is the same as shown in .

Specific examples of the sensitizing dye represented by the general formula [A] used in the present invention are shown below. 7-The following monetary items\12.ノ/CCTo)3sO? CCH2)3sO3Na(shiH2),L;UU-(niH2J,L;UOH
-1O A-13 A-14 When the silver halide emulsion according to the present invention is used as a green-sensitive emulsion, it is preferable to perform spectral sensitization with a sensitizing dye represented by the following general formula [B].

General Formula [B] In the formula, Zll and 2.1 each represent an atomic group necessary to form a benzene ring or a naphthalene ring fused to an oxazole.

The heterocyclic nucleus formed may be substituted with various substituents, and these preferred substituents are halogen atoms, aryl groups, alkyl groups, or alkoxy groups. More preferred substituents are a halogen atom, a phenyl group, and a methoxy group, and the most preferred substituent is a phenyl group.

According to a preferred embodiment of the invention, 211 and Zll
both represent a benzene ring fused to an oxazole ring, and at least one of these benzene rings has a
The 5-position of one benzene ring is substituted with a phenyl group, or the 5-position of one benzene ring is substituted with a phenyl group, and the 5-position of the other benzene ring is substituted with a halogen atom.

821 and R1! each represents an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group.

More preferably, R21 and R2 are each a carboxyl group or an alkyl group substituted with a sulfo group, most preferably a sulfoalkyl group having 1 to 4 carbon atoms. Most preferred is a sulfoethyl group.

R23 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group.

x and e represent anions, such as chlorine, bromine, CH3
Examples include anions such as SO4 and C2H8SO4.

n represents 1 or O. However, when the compound forms an inner salt, n represents 0.

Specific examples of the sensitizing dye represented by the general formula [B] that are preferably used in the present invention are shown below.

Margin below -I B-6 (CHx) 4 So 3 Na When the silver halide emulsion according to the present invention is used as a red-sensitive emulsion, one sensitizing dye represented by the following general formula [C] or the following general formula [ It is preferable to perform spectral sensitization using a sensitizing dye represented by [0].

General formula [C] General formula [D] In the formula, R represents a hydrogen atom or an alkyl group, R+ to R4 represent an alkyl group and an aryl group, respectively, and Z 1
12 112 4 and 2 are fused to a thiazole ring or selenazole ring, respectively, and I represents an atomic group necessary to form a benzene ring or a naphthalene ring, and Z represents a hydrocarbon atomic group necessary to form a 6-membered ring. , where a is l or 2
, Z represents a sulfur atom or a selenium atom, and Xe represents an anion.

In the above general formula, the alkyl group represented by R includes a methyl group, an ethyl group, and a propyl group, and R is preferably a hydrogen atom, a methyl group, or an ethyl group. Particularly preferred are a hydrogen atom and an ethyl group.

In addition, R , , R , , R , and R 4 are each a linear or branched alkyl group (this alkyl group may have a substituent. For example, methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxyethyl, Acetoxyethyl, carboxymethyl, carboxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, β-hydroxy=γ-sulfopropyl, sulfatepropyl, allyl, benzyl, etc.) or aryl group (this aryl group has a substituent) (for example, phenyl, carboxyphenyl, sulfophenyl, etc.), and the heterocyclic nucleus formed by zI+22+2 and Z may have a substituent, and preferred substituents is a halogen atom, an aryl group, an alkyl group, or an alkoxy group, and more preferably a halogen atom (for example, a chlorine atom), a phenyl group, or a methoxy group.

CH3SO4, CJsSOa, etc.), and Q represents 1 or 2.

However, when the compound forms an inner salt, a represents 1.

Typical specific examples of the sensitizing dyes represented by the general formulas [C] and [D] that are preferably used in the present invention are shown below.

2H6Ut”°1・r C-, -6-I D-2 The above general formula [A], [B], [C] or [
The amount of the sensitizing dye represented by D] is not particularly limited, but is approximately 1% silver halide 4 parts I; 1 x 10-'
- It is preferably used in the range of 1 x 10-"%, more preferably 5 x 10-@ to 5 x 10-
'It's a mole.

As a method for adding the sensitizing dye, a method well known in the art can be used.

For example, these sensitizing dyes can be dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents), in some cases diluted with water, and If necessary, they can be dissolved in water and added in the form of these solutions.

It is also advantageous to use ultrasonic vibrations for this dissolution. Further, the sensitizing dye used in the present invention is described in US Pat.
469.987, in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added, as described in Japanese Patent Publication No. 46-24185, etc. A method may also be used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added. Furthermore, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method.
The method of adding it is described in U.S. Patent No. 2,912.345,
, 342.605, 2,996.287, 3,
425.835 and the like can also be used.

The sensitizing dyes to be contained in the silver halide emulsion of the present invention may be dissolved in the same or different solvents, and these solutions may be mixed or added separately prior to addition to the silver halide emulsion. . When adding them separately, the order, time, and interval can be arbitrarily determined depending on the purpose. The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion manufacturing process, but it is preferably added during or after chemical ripening, and more preferably during chemical ripening.

The photosensitive material of the present invention having the above structure can be, for example, color negative and positive films, color photographic paper, etc., but especially when used in color photographic paper for direct viewing, the method of the present invention may be used. The effects of this will be effectively demonstrated.

The photosensitive materials of the present invention, including this color photographic paper,
It may be for single color or multicolor.

In the case of multicolor light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually used as photographic couplers. Although it has a structure in which layers are layered on top in an appropriate number and order of layers, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

When the photosensitive material used in the present invention is a multicolor photosensitive material, the specific layer structure includes a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer, Particularly preferred is an arrangement of an interlayer, a cyan dye image-forming layer, an interlayer, and a protective layer.

The dye image-forming coupler used in the present invention is not particularly limited, and various couplers can be used, but the compounds described in the following patents are included as representative examples.

Yellow dye image-forming couplers include acylacetamide type and benzoylmethane type 4-equivalent or 2-equivalent couplers, which are described, for example, in U.S. Pat. No. 2,778.65.
No. 8, No. 2,875.057, No. 2,908.573
No. 2,908.513, No. 3,227.155, No. 3,227,550, No. 3,253.924,
3,265.506, 3,277.155, 3,341.331 1, 3,369.895, 3,384.657, 3,408.194, 3
, No. 415,652, No. 3,447.928, No. 3,
551.155, 3,582.322, 3,7
25.072, German Patent No. 1,547.868, German Patent No. 2,057,941, German Patent No. 2,162.899, German Patent No. 2
, 163.812, 2,213.461, 2,
No. 219.917, No. 2,261.361, No. 2,2
No. 63,875, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 4
No. 8-29432, No. 48-66834, No. 49-1
No. 0736, No. 49-122335, No. 50-288
No. 34, No. 50.132926, No. 55.14424
No. 0 and No. 56-87041.

The magenta dye image-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers such as 5-pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, indasilone, and cyanoacetyl. Patent No. 2,600.788, No. 3,
No. 061,432, No. 3,062.653, No. 3,1
27.269, 3,311.476, 3,15
No. 2.896, No. 3,419.391, No. 3,519
．． No. 429, No. 3,555.318, No. 3,684.
No. 514, No. 3,705.896, No. 3, 888
.

No. 680, No. 3,907,571, No. 3,928.0
No. 44, No. 3,930°861, No. 3,930.81
No. 6, No. 3,933.500, JP-A-49-2963
No. 9, No. 49-111631, No. 49-129538
No. 51-112341, No. 52-58922,
No. 55-62454, No. 55-118034, No. 5
No. 6.38643, No. 56-135841, Special Publication No. 4
No. 6-60479, No. 52-34937, No. 55-2
No. 9421, No. 55-35696, British Patent No. 1,24
7.493, Belgian patent no. 769.116, West German patent no. 2.156. Issues of ll1, Special Publication Showa 46-6047
No. 9, JP-A-59-125732, JP-A No. 59-2282
No. 52, No. 59-162548, No. 59-17195
No. 6, No. 60-33552, No. 60-43659,
West German Patent No. 1,070.030 and U.S. Patent No. 3,725
．． It is described in each issue of No. 067.

Typical cyan dye image-forming couplers include phenolic and naphthol-based 4-equivalent or 2-equivalent type cyan dye image-forming couplers, and are described in U.S. Pat. No. 362.598,
2,367.531, 2,369.929, 2,423.730, 2,474.293, 2
, 476.008, 2,498.466, 2,
No. 545.687, No. 2,728.660, No. 2,7
72.162, 2, 895, 826, 2,
976.146, 3,002.836, 3,4
No. 19.390, No. 3,446.622, No. 3,47
No. 6.563, No. 3,737.316, No. 3,758
．． No. 308, No. 3,839.044, British Patent No. 478
, No. 991, No. 945.542, No. 1,084.48
No. 0, No. 1,377.233, No. 1,388,024
No. 1,543゜040, and Japanese Unexamined Patent Publication No. 4
No. 7-37425, No. 50-10135, No. 50-2
No. 5228, No. 50-112038, No. 50-117
No. 422, No. 50-130441, No. 51-6551
No. 51-37647, No. 51-52828, No. 51-108841, No. 53-109630, No. 5
No. 4-48237, No. 54-66129, No. 54-1
No. 31931, No. 55-32071, No. 59-146
No. 050, No. 59-31953 and No. 60-1172
It is described in each issue of No. 49.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has a carbon number of 8 or more. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. It may be either 2-equivalent.

It is advantageous to use gelatin as the binder (or protective colloid) used in the photosensitive material of the present invention, but
In addition, gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives,
Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as single or copolymers can also be used.

The photosensitive material of the present invention includes a hardening agent, a color clouding prevention agent,
lIgI! Additives such as stabilizers, ultraviolet absorbers, plasticizers, latex, surfactants, matting agents, lubricants, and antistatic agents can be used as desired.

An image can be formed on the photosensitive material of the present invention by subjecting it to a color development process known in the art.

The color developing agents used in the color developing solution of the present invention include aminophenol and p-phenylenediamine derivatives that are widely used in various color photographic processes.

The color developing solution applied to the photosensitive material of the present invention includes:
In addition to the M1 class aromatic amine color developing agent described above, known developer component compounds can be added.

The pH value of the color developer is usually above 7, most commonly about 10 to 13.

Color development temperature is usually 15°C or higher, generally 20°C.
~50°C. For rapid development, it is preferable to carry out the process at 30°C or higher. In addition, conventional processing takes 3 to 4 minutes.
However, the color development time of the present invention for the purpose of rapid processing is generally preferably carried out in the range of 20 seconds to 60 seconds, more preferably in the range of 30 seconds to 50 seconds.

After color development, the photosensitive material of the present invention is subjected to a bleaching process and a fixing process. Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments are not limited thereto.

Example 1 Various blue-sensitive silver halide emulsions were prepared by the method shown below. 2% gelatin aqueous solution kept at 40℃ 101
In 00O, add the following (liquid A) and (liquid B) to pAg=
6.5, p) While controlling l=3.0, add simultaneously over 30 minutes, and then add the following (solution C) and (solution D) to pAg=
7.3 and pH = 5.5, the simultaneous addition was carried out over 180 minutes. At this time, the control of pAg is
-45437, and the pH was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Liquid A) NaC23.42g KBr O.03g
Add H and O and add 200aQ (Liquid B) AgNOs 10g
Add H3O 200+
a(2(C liquid) NaCa
102-7gKBr
1.0g5
R-5 (methanol solution) 15.5
+aQH, add O 60
0m12 (D liquid) AgNOs
Add 300gH,0
After adding 600 mQ, add 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and 20% magnesium sulfate.
After desalting using an aqueous solution, it is mixed with an aqueous gelatin solution to obtain an average particle size of 0.85 μm and a coefficient of variation (σ/r) =
A monodisperse cubic emulsion EMP-1 having a silver chloride content of 99.5 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50°C for 90 minutes using the following compound, and blue-sensitive silver halide emulsion (E
M-A) was obtained.

Ammonium thiocyanate 30 mg 1 mol AgX
Sodium thiosulfate 0.8 mg 1 mol Ag
X Chloroauric acid 0.5a + g 1 mol AgX stabilizer 5B-16X 10-4 mos 1 mol AgX sensitizing dye D-15X 10-' mol/+ AgX sensitizing dye D-25X to-'Morph'+
(A liquid), (
The table shows the addition/non-addition of the compound represented by the general formula (S), chemical ripening conditions, sensitizing dyes, etc. of the halogen composition in liquid C).
EMB-1-EMB-12 by changing as shown in 1.
A blue-sensitive silver halide emulsion was prepared. (EMB-1
In Example 2, D-2 was used as the sensitizing dye. ) - F ((J+ri!SO1' (CIri3SO3H obtained I
Coating was carried out using an emulsion in the following configuration.

Each layer having the structure shown in Table 2 was coated on a support laminated with polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side to produce a multilayer silver halide color photograph. A photosensitive material was produced. The coating solution was prepared as follows.

1st layer coating liquid Yellow coupler (Y-1) 26.7g, dye image stabilizer (ST-1) IO, Og, dye image stabilizer (
ST-2) 6.7g, stain inhibitor (IQ-1) 0
．． Ethyl acetate 60IIIQ was added to and dissolved in 67 g and 6.7 g of high boiling point organic solvent (DNP), and this solution was diluted with lθ%
A yellow coupler dispersion was prepared by emulsifying and dispersing the mixture into 200 sQ of a 10% gelatin aqueous solution containing sodium alkylnaphthalene sulfonate l□sff using an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution. The following H-1 and H-2 were used as hardeners, and the following S-1 and S-2 were used as coating aids.

1. ′-・- Below ゛Margin s -1c, o, ′ Heat C1hCOOCHtCHC4H! 5-2CIbCOOCH*(CFxCFz)zHCHC
OOCHz (CFxCFa)zHSo, Na Q H2C (CIl!5OICH-CHx) i Below Margin Table-2-1 Table-2-2 1, ++/ Q C-2 ST-1 ST-2 V-1 CslL + (t ) V-2 DOP (dioctyl 7-talate) DNP (dinonylphthalate) DIDP (diisodecyl phthalate) pvp (
polyvinylpyrrolidone) us L
;H.

I-1 I-2 These samples were subjected to sensitometry using a conventional method, and during exposure, the temperature of the photosensitive needle and surroundings was set to I O'Cl2O℃, 3
After changing the temperature to 0°C and performing sensitometry, treatment was performed according to the following treatment steps.

The results of sensitometry are shown in Table 3.

The sensitivity is the relative sensitivity, and the gradation is the slope tan value of the sensitometric curve between 0.5 and 1.5. Reflection density was measured. (Using blue filter) [Processing step 1 Temperature Time color development
Bleach fixing at 35.0±0.3°O for 45 seconds
35.0±0.5℃ Stabilized for 45 seconds 30~3
4°0 90 seconds dry 60~
80°0 60 seconds *Fog was measured on an unexposed sample processed with the above color development for 90 seconds.

[Color developer] Pure water
800m (2 triethanolamine
10g N,N-diethylhydroxylamine
5g potassium bromide 0.0
2g potassium chloride 2g potassium sulfite 0.3g 1-human U
xyethylidene-1,1-di-wood sulfonic acid
1.0g ethylenediaminetetraic acid H1,
0g Catechol-3,5-disurunenic acid disodium salt
1.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g optical brightener (4,4'
-diaminostilbendisulfonic acid derivative)
1.0g potassium carbonate
Add 27g water to make total volume 1Q, pH = 10.10
Adjust to.

[Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% water flF[) 100-g Ammonium sulfite (40% aqueous solution) Add 27.5s+Q water to make 1a, carbonate Pite 5.7 with potassium or glacial acetic acid
Adjust to.

[Stabilizing liquid 1 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid
2.0g ethylenediaminetetraacetic acid
1.0g ammonium hydroxide (20% aqueous solution)
3.0g ammonium sulfite
3.0g Fluorescent brightener (4,4°-diaminostilbene dibenzoic acid derivative) 1.5g Add water to make up to 1Q, and adjust the pH with sulfuric acid or potassium hydroxide.
= 7.0.

From Table 3, samples No. 1, No. 1, and 5.6.12 of the present invention are excellent in low fog and small variations in gradation with respect to temperature changes during exposure. Among them, gold chloride is added during chemical sensitization,
Sample No. 1.6 using D-1 as the sensitizing dye
is clearly more sensitive and superior.

In contrast, samples in which the compound of the present invention was not used during grain formation were inferior in sensitivity, fog, and gradation variation. In addition, it was found that sample No. 9° to tt, in which the CQ content of silver halide grains was low, had a soft tone overall and was poor in suitability for rapid processing.

Example 2 Various green-sensitive silver halide emulsions were prepared by the method shown below.

[Preparation method of green-sensitive silver halide emulsion] (Liquid A) and (B
The average particle size was 0 in the same manner as EMP-1 except that the addition time of liquid) and the addition time of (liquid C) and (liquid D) were changed.
．． A monodisperse cubic emulsion EMP-2 was obtained with a diameter of 43 μm, a coefficient of variation (σ/r) of 0.08, and a silver chloride content of 99.5 mol %.

For EMP-2, the following compound was used at 120°C at 55°C.
A green-sensitive silver halide emulsion (EMG-
2) was obtained.

Other emulsion conditions are shown in Table 4, but the suppressor was added to (Liquid A) and (Liquid C) at a ratio of 1:10/% Silver Rorodide solvent was added 1 minute after adding chloroauric acid. Add it later.

Sodium thiosulfate 1.5mg/mol AgX
Chloroauric acid 1.0 mg 1 mol AgX
Stabilizer 5R-56X 10-'11 mole AgX sensitizing dye D-3 and D-44, OX 10-'l/l
A multilayer sample was prepared by replacing the AgX emulsion with the green-sensitive emulsion in the third layer of Example 1, and a similar test was conducted. The contents and results are shown in Table 4.

A green filter was used for the measurement.

Example 3 Various red-sensitive silver halide emulsions were prepared by the method shown below.

[Preparation method of red-sensitive silver halide emulsion] (Liquid A) and (B
The average particle size was 0 in the same manner as EMP-1 except that the addition time of liquid) and the addition time of (liquid C) and (liquid D) were changed.
．． A monodisperse cubic emulsion EMP-3 having a coefficient of variation of 50 μ-1 (Ce/r)-0.08 and a silver chloride content of 99.5 mol% was obtained.

EMP-3 was chemically ripened at 60°C for 90 minutes using the following compounds to form a red-sensitive silver halide emulsion (EMR-1).
) to get.

Other emulsion conditions are shown in Table 5, but the method of adding the inhibitor and silver halide solvent was the same as in Example 2.

Sodium thiosulfate 1, 8 mg 1 mol 1 mol A Auric acid 2.0 mg 1 mol 1 mol A fixative 5B-56X 10-' mol 1 mol Ag
X-sensitizing dyes D-51 and D-(i 8
．． Ox IQ-'i 1 mol Ag

Table 5 shows the contents and results. A red filter was used for the measurement.

Margin Example 4 The blue-sensitive, green-sensitive, and red-sensitive silver halide emulsions prepared in Examples 1, 2, and 3 were coated with the configurations shown in the table below to prepare multilayer samples.

However, for sample No. 47, 20 KBr was added to the coating solution for the first layer (blue sensitive layer), third layer (green sensitive layer), and fifth layer (red sensitive layer).
0+sg, 100 g%, prepared by adding 100 g,
Painted.

Next, a test was conducted in the same manner as in the above example.
. - Content results are shown in Table 6.

Okiichi Margin ☆、・ Example-5 A multilayer sample was prepared by preparing the following silver halide emulsion.

1000 μa of a 2% gelatin aqueous solution at 70°C was diluted with sulfuric acid (IN
) to adjust the pH to -2.0, the following silver halide solvent (1%) was added to 2.5a.

(silver halide solvent) C.B.

Further, while maintaining the temperature at 70°C, the following (H solution)
and (H solution) were added simultaneously over 15 minutes, and then (G solution) was added simultaneously.
Solution) and Solution H were added simultaneously over 70 minutes.

(H solution) Add NaCQl, 72g +1□0 and 150mf
f (H solution) AgNO35g Add H and O 150III
Q (G liquid) KBr
O,8gNaCQ
40.9g5R-5
(Methanol solution) Add 20BH20 320a+Q (H solution) hgNOs 120gH
, O and added 320 m (1) 5 minutes after the addition was completed, the temperature was lowered to 40 °C over 30 minutes, and desalination was performed in the same manner as in EMP-1 above.
A monodispersed cubic silver chlorobromide emulsion EMP-4 having an average grain size of 0.9 μm and a coefficient of variation (σ/r) of 0.09 and a silver chloride content of 99 mol % was obtained in accordance with ptl=6.0.

To EMP-4, sensitizing dye D-7 (added ff17.
The above E except that OX 10-' mol 1 mol AgX)
Chemical ripening was performed in the same manner as MB-1 to obtain blue-sensitive silver halide emulsion EMB-13.

By adjusting the addition time of (H solution) and (H solution) and (G solution) and (H solution) in the preparation method of EMP-4, EMP-5 (SR-555 mg) and EMP-6 were prepared.
(SR-560mg) was prepared. The results are shown in the table below.

For EMP-5, sensitizing dye D-8 (addition amount: 4,
Qx IQ-'+ru/lAgX)
7. Same as above, chemical ripening was carried out to form a green-sensitive emulsion EMG-
I got 18.

For EMP-6, sensitizing dye D-9 (addition amount: 1,
EMR- except Qx 10-'l/l AgX)
Chemical ripening was carried out in the same manner as in step 6 to obtain red-sensitive emulsion EM-15.
I got it.

The obtained emulsions were coated with the layer configurations shown in Tables 7-1 and 7-2 to prepare seven types of multilayer samples. When the samples were subjected to the same tests as in Examples 1 to 4, they reproduced the effects of the present invention and were found to be excellent silver-rodanide color photographic materials. , -1, the additional value is 0.189/ra'' DBP (dibutyl phthalate) TOP (trioctyl phosphate) TCP
() licresyl phosphate) TINP (triisononyl phosphate) PU^ (acrylic modified copolymer of polyvinyl alcohol) Eight! -3 I-4 Q-2 T-5 T-6 V-3 1;4II! (t) UV-4 UV-S -O CI! μ Q T-7 T-8 11$1 LH3 and H 5T-9 ST-10 Cu.

T-11 Q-3 HI-5 I-6 I-7 I-8 Kiri38 bus
8-9 l-10 [Effects of the Invention] As explained above, the silver rodanide photographic light-sensitive material of the present invention has high sensitivity, low fog, and extremely small gradation fluctuations with respect to temperature changes during exposure. In addition to being an excellent photosensitive material, it is also a photosensitive material for printing that has greatly improved suitability for rapid processing.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the silver halide emulsion layer have a silver chloride content of 90 mol%. In the above silver halide grains, a compound represented by the following general formula is present at any time from the time of grain formation to the start of desalting, and at least one of the silver halide solvents is present at any time during the chemical sensitization process. A silver halide photographic light-sensitive material, characterized in that it is prepared by adding one type of silver halide. General formula [S] ▲ Numerical formulas, chemical formulas, tables, etc. It represents an atomic group, and M represents a hydrogen atom or a cation. ]